Multistep Reaction Energy Profile (College Board AP® Chemistry): Study Guide
Multistep reaction energy profile
The energy changes that occur in reactions involving a multistep mechanism can be shown in a graph
A multistep energy profile can be used to:
Identify the number of elementary reactions
Determine (or calculate) the activation energy of each step
Consequently, identifying the rate-limiting step
Identify the number of intermediates involved in the reaction
Determine (or calculate) the overall energy change or enthalpy change
For example, consider a hypothetical reaction given by the equation:
A + 2B → D ΔH > 0 (endothermic)
If the proposed mechanism for this reaction involves a two-step elementary reaction given as:
A + B ⇋ C (fast)
C + B → D (slow)
To sketch the profile from the mechanism:
Draw one hump for each elementary step
Give the slow (rate-limiting) step the largest activation energy and the fast step a small one
Put each intermediate in a trough between two humps
End the products above the reactants if ΔH is positive (endothermic) and below them if ΔH is negative (exothermic)
The energy profile for this reaction may look like this:
Multistep energy profile

An energy profile diagram for a two-step reaction showing the activation energy, overall enthalpy change, and the intermediate
From the graph above:
The number of steps involved in the reaction is indicated by the number of peaks
Each peak also represents an activated complex/transition state
The step with the largest activation energy (the biggest rise from a trough to the next peak) is the rate-limiting step
The number of intermediates is the number of troughs between peaks
The overall enthalpy change, ΔH, is indicated by the difference in energy between the products and the reactant
Examiner Tips and Tricks
The highest peak on the diagram is not always the step with the largest activation energy. Make sure to measure each step’s activation energy from the trough just before it (the reactants or an intermediate) up to the next peak (the transition state), and compare those heights
Worked Example
Consider the energy profile diagram for the hypothetical reaction whose equation is given below and answer the following questions
X + 2Y → P + Q
(a) Describe the overall reaction as exothermic or endothermic
(b) Suggest the number of intermediates involved in the overall reaction
(c) Suggest the number of elementary steps involved in the reaction mechanism
(d) Identify the rate-limiting step

Answers:
Answer (a)
The energy of the product is greater than the energy of the reactants
Therefore, the reaction is endothermic
Answer (b)
There are two intermediates in the reaction
These are indicated by the troughs labeled B and D
Answer (c)
There are three elementary steps in the reaction
These are indicated by the peaks labeled A, C and E
Answer (d)
The rate-limiting step is the reaction with the highest activation energy
Therefore, the rate-limiting step is the second step from B → D
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